Extended amine curing agents and epoxy resins cured therewith

ABSTRACT

A method for curing 1,2-epoxy resins wherein a 1,2-epoxy resin is mixed with an effective amount of an amine curing agent comprising a solution of a normally solid cured polyurethane elastomer in a 1,2-epoxy-interactive polyamine curing agent, whereby reaction of the amino hydrogens of the said polyamine with the epoxy groups in the epoxy resin will result in curing of the epoxy resin.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

This invention relates to curing agents for epoxy resins and moreparticularly to amines of the type heretofore known for use as curingagents for epoxy resins extended, in accordance with the presentinvention, by the incorporation thereinto of a solid elastomericpolyurethane. The solid elastomeric polyurethane is derived from anessentially difunctional aromatic diisocyanate, a high molecular weightisocyanate reactive polyether and a difunctional cross linking agentsuch as a diol or a diamine. The resulting composition is used to cureepoxy resins of the type heretofore known in the art.

2. Prior Art

It is known to use amines such as aliphatic or aromatic amines for thecuring of epoxy resins as shown, for example in Waddill U.S. Pat. No.4,139,524 and Marquis et al. U.S. Pat. No. 4,162,358. See also, thetextbook "Handbook of Epoxy Resins" by H. Lee and K. Neville, McGrawHill Book Co., 1967. There is significant technical literature on thissubject as illustrated, for example by a technical brochure entitled"Jeffamine® Polyoxypropyleneamines", Copyright 1978 by JeffersonChemical Company, Inc. Becker et al. U.S. Pat. No. 3,847,726 disclosessheet metal laminates wherein the binder is an epoxide formed by curingan epoxy resin with a multi-component curing mixture, one component ofwhich is a Mannich Condensate of polyoxypropylene amine, phenol andformaldehyde.

An extensive body of technical knowledge has arisen relating to thepreparation of essentially solid polyurethane elastomers. See, forexample, Vols. I and II of "Polyurethane Chemistry and Technology" byJames H. Saunders and Kent C. Fish, Interscience Publishers, 1962 and1964. One such group of elastomers is frequently referred to as RIMpolyurethanes. This is an art-recognized term because RIM is an acronymfor "Reaction Injection Molding", which is not a material, but rather, aprocess for molding polyurethanes. In the reaction injection molding(RIM) process two highly reactive streams of chemicals are broughttogether under high pressure (i.e., 2000 psi) in a small mixing chamberwhere the streams are impingement mixed by being sprayed directly intoeach other. The mixed material flows immediately into a warm mold wherethe chemical reaction is completed and the part is cured. The resultantelastomeric polyurethane will contain small pores and voids so that itis not, technically speaking, a voidless solid material. For example itcan be calculated that the theoretical density for a polyurethaneelastomer should be about 70 pounds per cubic foot. Normally, RIMelastomers based upon polyurethanes will have a density in the order ofmagnitude of about 60 pounds per cubic foot. The RIM process and the rawmaterials used therein are described in greater detail in the text,"Reaction Injection Molding" edited by Walter E. Becker, Van NostrandReinhold publishers, 1979.

In reaction injection molding, one of the two streams referred to aboveis the essentially difunctional aromatic diisocyanate stream.

The other stream is a stream containing a high molecular weightisocyanate reactive polyether based on propylene oxide, a cross linkersuch as a diol or a diamine and other conventional additives.

A representative list of U.S. patents directed to the preparation ofRIM-polyurethanes includes, for example McDaniel et al. U.S. Pat. No.4,243,760, Dominguez et al. U.S. Pat. No. 4,254,069, Dominguez U.S. Pat.No. 4,273,884, Dominguez et al. U.S. Pat. No. 4,273,885, Gilbert et al.U.S. Pat. No. 4,297,444, Cuscurida et al. U.S. Pat. No. 4,301,110,Cuscurida et al. U.S. Pat. No. 4,309,532, Dominguez et al. U.S. Pat. No.4,350,778, and McEntire et al. U.S. Pat. No. 4,359,540. Also, Cuscuridaet al. U.S. Pat. No. 4,358,547 and Dominguez et al. U.S. Pat. No.4,362,824.

Solid elastomeric polyurethanes such as RIM polyurethanes are normallyused as utilitarian articles such as body parts for automobiles, etc.The resultant scrap and defective moldings present a serious disposalproblem. For example an article "The Reclamation of FlexiblePolyurethane Foam" found in the Polymer-Plas. Technol. Eng., 19(1), 1-20(1982), discloses various techniques that have been conceived insofar asthe reclamation of highly porous, low density flexible polyurethane foamis concerned. Reclamation of high density polyurethane elastomerspresents special problems because of the strength and durability of thematerials involved.

Among the techniques for reclamation mentioned in this article is theuse of a glycol or an amine as a solvent. As another example, in Lidy etal. U.S. Pat. No. 4,267,078, a process for disposing of scrappolyurethane is disclosed which involves comminuting the polyurethaneand reacting it with an alkylene oxide to form a product that can beused to form additional foamed polyurethane. British specification No.1,595,431 discloses a method wherein a polyurethane is comminuted,melted and then molded into elastomeric polyurethane products such asshoe soles. U.K. patent application No. 2,062,660A is directed to areclaiming method wherein the polyurethane is heated in the presence ofa compound capable of generating ammonia gas on decomposition in orderto provide a degradation product.

SUMMARY OF THE INVENTION

In one aspect the present invention is directed to modified (i.e.,extended) amine curing agents which are prepared by dissolving a solidelastomeric polyurethane such as a RIM polyurethane in an amine of thetype used for curing epoxy resins. The RIM polyurethane can beincorporated into the amine by comminuting the RIM polyurethane andadding this to the amine at an elevated temperature such as atemperature within the range of about 100° to about 200° C.

In an alternate procedure that is particularly useful when theelastomeric polyurethane is not more than sparingly soluble in theamine, the RIM polyurethane is dissolved in an organic solvent at atemperature in the range of about 100° to about 200° C. The resultantsolution is mixed with the amine and then the solvent is stripped fromthe resultant mixture by any conventional means, such as vacuumdistillation, to provide the desired extended amine curing agent.

When the solution of the RIM polyurethane in the amine is cooled, itsometimes happens that phase separation into a plurality of liquidphases will occur. This is a function of the amine used as a solvent andalso of the concentration of RIM polyurethane in the amine solution.Phase separation is not detrimental to the overall utility of theextended amine curative since the amine curing agent and epoxy startingmaterial are normally mixed with agitation at the time of use. However,if phase separation is considered bothersome, it can be eliminated inmost instances by using the amine as a solvent for the RIM polyurethaneand then making a Mannich Condensate with the amine urethane solution.

In another aspect the present invention is directed to the use ofextended amine curing agents for curing epoxy resins.

DETAILED DESCRIPTION

The principal components of the compositions and methods of the presentinvention are the epoxy resin, the amine curing agent and the solidelastomeric polyurethane that is dissolved in the amine.

EPOXIDE STARTING MATERIALS

Generally the vicinal epoxide compositions that can be cured using thecuring agents of this invention are organic materials having an averageof more than one reactive 1,2-epoxide group. These polyepoxide materialscan be monomeric or polymeric, saturated or unsaturated, aliphatic,cycloaliphatic, aromatic or heterocyclic, and may be substituted ifdesired with other substituents besides the epoxy groups, e.g., hydroxylgroups, ether radicals, halogenated phenyl groups and the like.

The most widely used epoxy resins are diglycidyl ethers of bisphenol A:##STR1## where n represents a number from 0 to 5.

However, these epoxides are representative of the broader class ofepoxide compounds that are useful in making epoxy resins.

A widely used class of polyepoxides that can be cured according to thepractice of the present invention includes the resinous epoxy polyethersobtained by reacting an epihalohydrin, such as epichlorohydrin, and thelike, with either a polyhydric phenol or a polyhydric alcohol. Anillustrative, but by no means exhaustive, listing of suitable dihydricphenols includes 4,4'-isopropylidene bisphenol,2,4'-dihydroxydiphenylethylmethane,3,3'-dihydroxydiphenyldiethylmethane,3,4'-dihydroxydiphenylmethylpropylmethane,2,3'-dihydroxydiphenylethylphenylmethane, 4,4'-dihydroxydiphenylmethane,4,4'-dihydroxydiphenylbutylphenylmethane,2,2'-dihydroxydiphenylditolylmethane,4,4'-dihydroxydiphenyltolylmethyl-methane and the like. Other polyhydricphenols which may also be co-reacted with an epihalohydrin to providethese epoxy polyethers are such compounds as resorcinol, hydroquinone,substituted hydroquinones, e.g., tertbutylhydroquinone, and the like.

Among the polyhydric alcohols that can be co-reacted with anepihalohydrin to provide the resinous epoxy polyethers are suchcompounds as ethylene glycol, propylene glycol, butylene glycols,pentane diols, bis(4-hydroxycyclohexyl)dimethylmethane,1,4-dimethylolbenzene, glycerol, 1,2,6-hexanetriol, trimethylolpropane,mannitol, sorbitol, erythritol, pentaerythritol, their dimers, trimersand higher polymers, e.g., polyethylene glycols, polypropylene glycols,triglycerol, dipentaerythritol and the like, polyallyl alcohol,polyhydric thioethers, such as 2,2'-, 3,3'-tetrahydroxydipropylsulfideand the like, mercapto alcohols such as α-monothioglycerol,α,α'-dithioglycerol, and the like, polyhydric alcohol partial esters,such as monostearin, pentaerythritol monoacetate, and the like, andhalogenated polyhydric alcohols such as the monochlorohydrins ofglycerol, sorbitol, pentaerythritol and the like.

Another class of polymeric polyepoxides that can be cured by means ofthe above-described curing agents includes the epoxy novolac resinsobtained by reacting, preferably, in the presence of a basic catalyst,e.g., sodium or potassium hydroxide, an epihalohydrin, such asepichlorohydrin, with the resinous condensate of an aldehyde, e.g.,formaldehyde, and either a monohydric phenol, e.g., phenol itself, or apolyhydric phenol. Further details concerning the nature and preparationof these epoxy novolac resins can be obtained in Lee, H. and Neville, K."Handbook of Epoxy Resins".

It will be appreciated by those skilled in the art that the polyepoxidecompositions that can be cured according to the practice of the presentinvention are not limited to the above described polyepoxides, but thatthese polyepoxides are to be considered merely as being representativeof the class of polyepoxides as a whole.

The amount of curing agent that is employed in curing polyepoxidecompositions will depend on the amine equivalent weight of the curingagent employed. The total number of equivalents of amine group ispreferably from about 0.8 to about 1.2 times the number of epoxideequivalents present in the curable epoxy resin composition with astoichiometric amount being most preferred.

Various conventionally employed additives can be admixed with thesepolyepoxide-containing compositions prior to final cure. For example, incertain instances it may be desired to add minor amounts of otherco-catalysts, or hardners, along with the curing agent system hereindescribed. Conventional pigments, dyes, fillers, flame retarding agentsand other compatible natural and synthetic resins can also be added.Furthermore, known solvents for the polyepoxide materials such asacetone, methyl ethyl ketone, toluene, benzene, xylene, dioxane, methylisobutyl ketone, dimethylformamide, ethylene glycol monoethyl etheracetate, and the like, can be used if desired, or where necessary.

THE AMINE CURING AGENT

A curable epoxy resin composition is prepared by admixing one or moreepoxides, as described above, with an epoxy-interactive polyamine curingagent. The ratio of active amino hydrogens to epoxy groups in theadmixture may suitably be in the range of about 0.5-2:1 and, preferably,in the range of about 0.8-1.5:1.

Suitable polyamine curing agents are those that contain more than twoactive hydrogens per molecule. Examples of such curing agents arealkylene polyamines represented by the formula:

    NH.sub.2 C.sub.2 H.sub.4 (NHC.sub.2 H.sub.4).sub.n X

where X is --OH or --NH₂ and where n has the value of 0 to about 5. WhenX is --NH₂, such alkylene polyamines include ethylene diamine,diethylene triamine, triethylene tetramine, tetraethylene pentamine,pentaethylene hexamine, and the like.

These polyamines provide admixtures having low viscosity and provideepoxy resin compositions that generally have good chemical resistance.When X is --OH, representative amines include

    H.sub.2 NC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NHCH.sub.2 CH.sub.2 OH,

    H.sub.2 NCH.sub.2 CH.sub.2 NHC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NHCH.sub.2 CH.sub.2 OH

Long-chain polyamine adducts such as trimethyl-1,6-hexanediamine mayalso be used to impart color stability.

Thus, broadly speaking, aromatic, alicyclic, heterocyclic, and aliphaticamines may be used as well as more complex amine compounds such aspolyether polyamines, etc. Other examples includeN-aminoethylpiperazine, m-phenylenediamine, 2,4- or 2,6-toluenediamine,etc.

A particularly useful class of amines are amines derived frompolyoxypropylene diols and triols.

Preferably, we employ polyoxypropylene diamines of the formula:

    H.sub.2 NCH(CH.sub.3)CH.sub.2 --OCH.sub.2 CH(CH.sub.3)--.sub.x NH.sub.2

wherein x is an integer of from about 2 to about 40, andpolyoxypropylene triamines of the formula: ##STR2## wherein x, y and zrepresent integers in the range of about 1 to 15, and the sum of x, yand z is from about 3 to about 50. The most preferred polyoxypropylenediamines of the formula have average molecular weights between about230, where x is an average of 2.6 to about 2,000 where x is an averageof about 33.1. Preferred polyoxypropylene triamines of the above formulahave average molecular weights between about 190 to about 3,000. Thesepolyoxypropylene di- and triamines are readily available commercially ina wide variety of molecular weight ranges.

Also useful are amines having the formula:

    H.sub.2 NCH(CH.sub.3)CH.sub.2 [OCH(CH.sub.3)CH.sub.2 ].sub.x --[OCH.sub.2 CH.sub.2 ].sub.y --[OCH.sub.2 CH(CH.sub.3)].sub.z NH.sub.2

where x+z equals 2 to 10 and y is a number having a value from 1 to 50.

THE ELASTOMERIC (RIM) POLYURETHANE

As has been heretofore indicated, the elastomeric polyurethanes to beused as extenders in accordance with the present invention are preparedby the reaction of an essentially difunctional aromatic diisocyanatewith a high molecular weight isocyanate reactive polyether based onpropylene oxide.

The polyethers useful in making the polyurethane elastomers includepolyether polyols, polyester diols, triols, tetrols, polyetherpolyaminesetc., having an equivalent weight of at least 500, and preferably atleast 1000 up to about 3000 or more. The polyether polyols based ontrihydric initiators of about 4000 molecular weight and above areespecially preferred. The polyethers may be prepared from lower alkyleneoxides such as ethylene oxide, propylene oxide, butylene oxide ormixtures of propylene oxide, butylene oxide and/or ethylene oxide.Propylene oxide is at least about 60 wt percent of the polyol component.When butylene oxide is used, propylene oxide may be omitted, if desired.In order to achieve the rapid reaction rates which are normally requiredfor molding RIM polyurethane elastomers, it is preferable that thepolyol be capped with enough ethylene oxide to increase the reactionrate of the polyurethane mixture. Normally at least 50% primary hydroxylis preferred, although amounts of primary hydroxyl less than this areacceptable if the reaction rate is rapid enough to be useful inindustrial application. Hydroxyl terminated quasi-prepolymers of polyolsand isocyanates are also useful in this invention.

The polyethers and polyesters that may be used are described in greaterdetail in the textbook edited by W. E. Becker, mentioned above. The useof polyether polyamines is disclosed, for example, in copendingDominquez et al. U.S. patent application Ser. No. 371,161 filed Apr. 3,1982.

The chain-extenders are preferably difunctional and include diols, aminoalcohols, diamines or mixtures thereof, such as 1,4-butanediol, ethyleneglycol, 1,4-cyclohexane diol, bis-hydroxyethylhydroquinone, etc. Amideor ester containing diols or amino alcohols, aromatic diamines andaliphatic amines are also suitable as chain-extenders.

A wide variety of aromatic polyisocyanates may be used. Typical aromaticpolyisocyanates include p-phenylene diisocyanate, polymethylenepolyphenylisocyanate, 2,6-toluene diisocyanate, dianisidinediisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate,bis(4-isocyanatophenyl)methane, bis(3-methyl-3-isocyantophenyl)methane,bis(3-methyl-4-isocyanatophenyl)methane, and 4,4'-diphenylpropanediisocyanate.

Other useful aromatic polyisocyanates are methylene-bridged polyphenylpolyisocyanate mixtures which have a functionality of from about 2 toabout 4. See, for example, U.S. Pat. Nos. 2,683,730; 2,950,263;3,012,008; 3,344,162 and 3,362,979.

The preferred aromatic polyisocyanate is methylenebis(4-phenylisocyanate) or MDI. Pure MDI, quasi-prepolymers of MDI,modified MDI, etc. and other materials of this type may be used toprepare suitable RIM elastomers. Since pure MDI is a solid and, thus,often inconvenient to use, liquid products based on MDI are often usedand are included in the scope of the terms MDI or methylenebis(4-phenylisocyanate) used herein. U.S. Pat. No. 3,394,164 is anexample of a liquid MDI product. Uretonimine modified pure MDI isincluded also. This product is made by heating pure distilled MDI in thepresence of a catalyst. The liquid product is a mixture of pure MDI andmodified MDI: ##STR3## Examples of commercial materials of this type areUpjohn's ISONATE® 125M (pure MDI) and ISONATE® 143L ("liquid" MDI).Preferably the amount of isocyanates used is the stoichiometric amountbased on all the ingredients in the formulation.

Tertiary amines that can be used as catalysts include trialkylamines(e.g., trimethylamine, triethylamine), heterocyclic amines such asN-alkylmorpholines (e.g., N-methylmorpholine, N-ethylmorpholine),dimethyldiaminodiethylether, 1,4-dimethylpiperazine, triethylenediamine,etc., aliphatic polyamines such asN,N,N',N'-tetramethyl-1,3-butanediamine, etc.

It has been found that an improvement in processing characteristics ofreaction injection molded (RIM) polyurethanes may be had by employmentof a combination catalyst. A combination catalyst comprising a weaktertiary amine catalyst, a fast gelation organo tin catalyst and adelayed action gelation organo tin catalyst can also be used. Forexample, the fast gelation tin catalyst may be dibutyltin dilaurate, thedelayed action gelation tin catalyst may be an alkyltin mercaptide suchas a commercial product known as FOMREZ®UL-29. The weak tertiary aminemay be methyldiethanolamine.

The RIM formulation may include other recognized ingredients such asadditional cross-linkers, catalysts, extenders, blowing agents, foamstabilizers, dyes, chipped or milled glass fibers, chopped or milledcarbon fibers and/or other mineral fibers, etc.

PREPARATION OF THE EXTENDED AMINE CURING AGENT

In accordance with the present invention, a polyurethane elastomer suchas a RIM elastomer is comminuted and then dissolved in an amine curingagent of the type described herein. This is a straight-forward operationthat can be performed in any suitable reaction vessel such as anautoclave provided with agitation means and means for heating thecontents of the clave. The desired quantity of the amine curing agent isplaced in the vessel and brought to a desired temperature with agitationnormally within the range of about 100° to 200° C., preferably under aninert atmosphere. The temperature to be utilized will be, in part, afunction of the temperature at which the urethane elastomer willdissolve. It has been found that this normally will occur at atemperature within the range of about 140° to about 170° C.

In some situations the resultant solution may tend to separate into twoor more layers. This does not present a problem so long as the layersare well mixed before the extended amine is added to the epoxy, ashereafter described. To the contrary, solutions that tend to layerfrequently improve the adhesion properties of the resultant epoxy.

In accordance with a modified procedure that is particularly useful whenthe elastomeric polyurethane is not soluble in the amine to be used as acuring agent or is only sparingly soluble, the comminuted elastomericpolyurethane is first dissolved in a polar organic solvent in which itis soluble such as dimethylformamide, glycol ethers such as ethyleneglycol, diethylether, ethylene glycol dibutylether, ethylene glycolacetates such as ethylene glycol diacetate, etc. This step is performedas described above with respect to the amine, in a suitable reactionvessel such as an autoclave and an appropriate temperature within therange of 100° to 200° C. After the solution is formed, it is mixed withthe desired amine curing agent and the solvent is then removed from theresultant mixture, for example, by vacuum distillation.

In situations where the use of the amine curing in the form of a MannichCondensate is desired, the procedures normally used in the preparationof Mannich Condensates are employed (see, for example, Becker U.S. Pat.No. 3,847,726). A phenol, preferably phenol, is used as the source ofthe active hydrogen for the reaction and is preferably used in anequimolar ratio to the formaldehyde. However, the mol ratio of the amineto the formaldehyde may be varied, as desired. Ratios of 1 to 4 mols ofamine per mol of formaldehyde have been used with success. Other phenolsthat can be used include, for example, alkylphenols such as nonylphenol,dialkylphenols, etc.

It is within the scope of the present invention to use known extendersfor amine-based epoxy using systems, for example, synthetic rubber suchas a rubbery liquid amine-terminated copolymer of acrylonitrile andbutadiene.

SPECIFIC EXAMPLES EXAMPLE 1

A series of extended amine curing agents were prepared by dissolving acomminuted RIM polyurethane in the desired amine in a resin kettle at anappropriate temperature with agitation and heating.

The particular elastomeric polyurethane used in this series ofexperiments was one which had been prepared by reacting apolyisopropylene polyetherpolyol having a functionality of 3 and amolecular weight of about 6500 with ethylene glycol in a liquidMDI-based isocyanate.

The amines that were used, the temperature of the solution and theamount of scrap incorporated are indicated in the following table.

                                      TABLE 1                                     __________________________________________________________________________    Amine.RIM Solutions Prepared                                                                    Amount Scrap                                                                          Temp.                                                                 RIM added,                                                                            required,                                           Run #                                                                             Amine         wt %    °C.                                                                         Remarks                                        __________________________________________________________________________    5409-31                                                                           JEFFAMINE D-230                                                                             16.7    170  --                                             5409-33                                                                           JEFFAMINE D-230                                                                             30      170  --                                             5409-35                                                                           JEFFAMINE D-230                                                                             20      170  --                                             5409-36                                                                           JEFFAMINE D-230                                                                             40      170  Two layers                                     5409-38                                                                           JEFFAMINE D-2000/D-400                                                                      20      220  --                                                 (3/1 blend)                                                               5409-41                                                                           N--aminoethylpiperazine                                                                     30      150  Two layers                                     5409-45                                                                           THANCAT ® DPA                                                                           10      170  --                                             5409-46                                                                           JEFFAMINE ED-900                                                                            20      170  --                                             5409-48                                                                           Triethylenetetramine                                                                        20      140  Two layers                                     5409-49                                                                           Isophoronediamine                                                                           20      150  --                                             5409-51                                                                           JEFFAMINE T-403                                                                             30      175  --                                             __________________________________________________________________________

JEFFAMINE D-230, D-400 and D-2000 are represented by the followingstructure:

    ______________________________________                                        H.sub.2 NCH(CH.sub.3)CH.sub.2 --[OCH.sub.2 CH(CH.sub.3)]--.sub.x NH.sub.2     JEFFAMINE      x (approx.)                                                    ______________________________________                                         D-2000        33.1                                                           D-400          5.6                                                            D-230          2.6                                                            ______________________________________                                    

JEFFAMINE T-403 has the following structure: ##STR4##

THANCAT DPA is represented by the following structure:

    [HOCH(CH.sub.3)CH.sub.2 ].sub.2 NCH.sub.2 CH(CH.sub.3)N(CH.sub.3).sub.2

Amines such as JEFFAMINE-ED 900 may be generically represented by theformula: ##STR5## wherein x plus z equal about 3.5 and y equals about 13to 46.

The physical properties of the resultant solutions were measured and theresults as set forth in Table 2.

Thereafter, the extended amines were used to cure a representative epoxyresin with the results set forth in Table 3. In one set of experimentsthe epoxy resin was cured at ambient temperature (Table 3) and inanother set of experiments the epoxy resin was cured at an elevatedtemperature. The results of the elevated temperature cure are set forthin Table 4.

                                      TABLE 2                                     __________________________________________________________________________    Typical Analyses of Amine.RIM Solutions                                                  5409-                                                                             5409-                                                                             5409-                                                                             5409-                                                                             5409-                                                                             5409-                                                                             5409-                                                                             5465-                                                                             5409-                                                                             5465-                                                                             5465-                                                                             5465-                                                                             5465-              Run No. 68A                                                                              31  35  33  36  68C 51  18  41  28A 28B 28C 28D                    __________________________________________________________________________    Amine      D-230                                                                             D-230                                                                             D-230                                                                             D-230                                                                             D-230                                                                             T-403                                                                             T-4.03                                                                            AEP AEP TETA                                                                              TETA                                                                              IPDA                                                                              IPDA               Wt % RIM   0   16.7                                                                              20  30  40  0   30  0   30  0   20  0   20                 Total acetylatables,                                                                     8.75                                                                              7.96                                                                              7.24                                                                              6.38                                                                              5.40                                                                              6.75                                                                              5.04                                                                              15.68                                                                             11.06                                                                             23.70                                                                             19.02                                                                             11.74                                                                             9.63               meq/g                                                                         Total amine, meq/g                                                                       8.45                                                                              6.74                                                                              6.40                                                                              5.22                                                                              4.04                                                                              6.45                                                                              3.87                                                                              23.50                                                                             16.15                                                                             24.44                                                                             19.63                                                                             11.89                                                                             8.92               1° Amine, meq/g                                                                   8.30                                                                              6.58                                                                              6.19                                                                              5.03                                                                              3.91                                                                              6.16                                                                              3.45                                                                              7.5 11.25                                                                             11.32                                                                             2.53                                                                              11.87                                                                             8.88               2° Amine, meq/g                                                                   --  --  --  --  --  --  --  --  --  10.66                                                                             15.11                                                                             0.01                                                                              0.02               3° Amine, meq/g                                                                   --  --  --  --  --  --  --  --  --  2.46                                                                              1.99                                                                              0.01                                                                              0.02               Specific gravity,                                                                        0.9480                                                                            0.9912                                                                            0.9976                                                                            1.0262                                                                            1.0525                                                                            0.9812                                                                            1.0500                                                                            0.9879                                                                            1.0529                                                                            0.9853                                                                            1.0268                                                                            0.9261                                                                            0.9800             20/20° C.                                                              Brookfield visc.,                                                                        --  62  97  455 4000                                                                              --  19400                                                                             20  672 --  --  --  --                 cps, 25° C.                                                            Water, wt %                                                                              0.10                                                                              0.15                                                                              0.15                                                                              0.19                                                                              0.08                                                                              0.08                                                                              0.04                                                                              0.57                                                                              0.15                                                                              1.78                                                                              0.34                                                                              0.17                                                                              0.08               __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    Properties of Epoxy Resin Cured with Solutions of                             RIM Urethane in JEFFAMINE Polyetheramines (Ambient Curing)                                     5409-68B                                                                           5409-31B                                                                           5409-35B                                                                           5409-33B                                                                           5409-36B                                                                           5409-68D                                                                           5409-51B                       __________________________________________________________________________    Formulation, pbw:                                                             Epoxy Resin (WPE 188)                                                                          100  100  100  100  100  100  100                            JEFFAMINE ® D-230                                                                          26.4 --   --   --   --   --   --                             D-230.RIM (83.3/16.7)                                                                          --   36   --   --   --   --   --                             D-230.RIM (80/20)                                                                              --   --   37.6 --   --   --   --                             D-230.RIM (70/30)                                                                              --   --   --   47   --   --   --                             D-230.RIM (60/40)                                                                              --   --   --   --   54.7 --   --                             JEFFAMINE T-403  --   --   --   --   --   36.4 --                             T-403.RIM (70/30)                                                                              --   --   --   --   --   --   62.5                           Accelerator 399  5    5    5    5    5    5    5                              Brookfield viscosity, cps, 25° C.                                                       850  1290 1790 3560 --   2200 14620                          (resin-curative mix)                                                          Gel time, min. (200 g mass)                                                                    52.0 56.0 46.5 55.0 --   52.5 ˜75                      Peak exothermic temp., °C.                                                              189.5                                                                              166.0                                                                              172.2                                                                              137.6                                                                              --   160.2                                                                              63.8                           Time to peak temp., min.                                                                       61.5 71.5 61.0 76.5 --   80.2 97.5                           Properties of cured 1/8" Castings.sup.1                                       Shore D hardness, 0-10 sec                                                                     90-89                                                                              80-78                                                                              78-77                                                                              77-75                                                                              75-74                                                                              90-88                                                                              76-75                          Ultimate elongation, %                                                                         2.1  3    3.9  10   6.9  1.7  6.5                            Heat deflection temp., °C.                                                              46/48                                                                              45/46                                                                              48/49.5                                                                            56.5/61.5                                                                          40/44                                                                              48/48.5                                                                            45/48                          264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                 0.23 0.28 0.39 0.82 0.31 0.42 0.38                           Tensile strength, psi                                                                          8900 7200 8300 9000 5000 7500 6600                           Tensile modulus, psi                                                                           498000                                                                             458000                                                                             459000                                                                             347000                                                                             516000                                                                             439000                              Flexural strength, psi                                                                         12000                                                                              13000                                                                              13000                                                                              14500                                                                              9800 16000                                                                              11000                          Flexural modulus, psi                                                                          495000                                                                             465000                                                                             484000                                                                             455000                                                                             377000                                                                             506000                                                                             412000                         Tensile shear adhesion, psi                                                                    1030 1280 1600 2770 2130 1470 2240                           Peel strength, pli                                                                             3.2  3.4  3.2  3.5  4.0  2.6  --                             __________________________________________________________________________     .sup.1 Cured 7 days ˜25° C.                                 

                                      TABLE 4                                     __________________________________________________________________________    Properties of Epoxy Resin Cured with Solutions of                             RIM Urethane in JEFFAMINE Polyetheramines (Elevated Temperature Curing)                        5409-68A                                                                           5409-31A                                                                           5409-35A                                                                           5409-33A                                                                           5409-36A                                                                           5409-68C                                                                           5409-51A                       __________________________________________________________________________    Formulation, pbw:                                                             Epoxy resin (WPE 188)                                                                          100  100  100  100  100  100  100                            JEFFAMINE ® D-230                                                                          32   --   --   --   --   --   --                             D-230.RIM (83.3/16.7)                                                                          --   42   --   --   --   --   --                             D-230.RIM (80/20)                                                                              --   --   44   --   --   --   --                             D-230.RIM (70/30)                                                                              --   --   --   55   --   --   --                             D-230.RIM (60/40)                                                                              --   --   --   --   64   --   --                             JEFFAMINE T-403  --   --   --   --   --   42   --                             T-403.RIM (70/30)                                                                              --   --   --   --   --   --   73                             Properties of cured 1/8" Castings.sup.1                                       Shore D hardness, 0-10 sec                                                                     88-86                                                                              73-72                                                                              78-76                                                                              76-74                                                                              74-72                                                                              83-82                                                                              75- 73                         Ultimate elongation, %                                                                         6.6  10.8 10.6 13   6.1  10.2 9.5                            Heat deflection temp., °C.                                                              80/83.5                                                                            77/81                                                                              74/78.5                                                                            69.5/74                                                                            63/70                                                                              78/82.5                                                                            70/76                          264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                 0.92 1.26 1.07 0.99 1.03 0.68 0.82                           Tensile strength, psi                                                                          9100 9300 8800 8600 8400 8800 8100                           Tensile modulus, psi                                                                           427000                                                                             427000                                                                             402000                                                                             393000                                                                             404000                                                                             395000                                                                             363000                         Flexural strength, psi                                                                         15000                                                                              16000                                                                              15000                                                                              14000                                                                              14000                                                                              14000                                                                              14000                          Flexural modulus, psi                                                                          424000                                                                             426000                                                                             408000                                                                             390000                                                                             402000                                                                             402000                                                                             378000                         Tensile shear adhesion.sup.2, psi                                                              4030 4060 2160 4230 3930 3920 4250                           Peel strength.sup.2, pli                                                                       2.3  2.3  2.3  11.6 17.7 3.5  16.9                           __________________________________________________________________________     .sup.1 Cured 2 hrs 80° C., 3 hrs 125° C.                        .sup.2 Cured 2 hrs 110° C.                                        

As will be seen from Table 3, satisfactory results were obtained in allinstances. There is a tendency for the extended systems to be somewhatsofter and to have lower heat deflection temperatures than systems curedwith amines alone. They are also more resistant to impact and are lessbrittle. These are advantageous properties which enhance the utility ofthe epoxy resins prepared from the extended amines of the presentinvention.

Note also that there was a steady increase in shear adhesion with theuse of increasing amounts of RIM material in the extended amine.

Insofar as Table 4 is concerned, there was generally very littledifference between the properties of the amine and the extended aminecured systems. The extended curing agents provided systems that wereslightly softer but more flexible. Also the compositions of the presentinvention improved the peel strength of the cured systems.

EXAMPLE 2

In a second comparative experiment about 20 weight percent of theelastomeric polyurethane was incorporated into Jeffamine ED-900 and anepoxy resin was cured with this composition in combination withn-aminoethylpiperazine. Results were compared with a similar epoxy resinsystem cured with a mixture of N-aminoethylpiperazine and JEFFAMINE,ED-900.

The results of this experiment are set forth in Table 5.

                  TABLE 5                                                         ______________________________________                                        Comparison of Systems Cured with                                              JEFFAMINE ED-900 or ED-900.RIM Solution as Co-Curative                                           5409-89A                                                                              5409-89B                                           ______________________________________                                        Formulation, pbw                                                              Epoxy Resin (WPE 188)                                                                              100       100                                            N--aminoethylpiperazine                                                                            15.8      15.8                                           JEFFAMINE ED-900     40        --                                             ED-900.RIM (80/20)   --        50                                             Properties of cured 1/8" Castings.sup.1                                       Shore D hardness, 0-10 sec                                                                         72-68     65-61                                          Ultimate elongation, %                                                                             67        38                                             Heat deflection temp., °C.                                                                  36.5/38.5 38/41                                          264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                     2.88      1.68                                           Tensile strength, psi                                                                              3800      3300                                           Tensile modulus, psi 207000    141000                                         Flexural strength, psi                                                                             6400      5400                                           Flexural modulus, psi                                                                              195000    146000                                         ______________________________________                                         .sup.1 Cured 2 hrs 80° C., 3 hrs 125° C.                   

Note from Table 5 that the heat deflection temperature was improved andthat a softer cured epoxy resin was formed.

EXAMPLE 3

In this series of examples, three extended amines were prepared, onebased upon aminoethylpiperazine, another based on triethylenetetramine(TETA), and a third based on isophoronediamine (IPDA). The solutionswere prepared in the manner described above in Example 1. The resultsobtained when these extended amines were used to cure an epoxy resin areset forth in Table 6.

                                      TABLE 6                                     __________________________________________________________________________    Properties of Epoxy Resin Cured with Solutions of                             RIM Urethane in Various Amines (Elevated Temperature Curing)                  __________________________________________________________________________                     5409-37B                                                                           5409-41A                                                                           5409-68A                                                                           5409-48A                                                                           5409-68C                                                                           5409-49A                                                                           5409-68D                                                                           5409-49B                  __________________________________________________________________________    Formulation, pbw:                                                             Epoxy Resin (WPE 188)                                                                          100  100  100  100  100  100  100  100                       N--aminoethylpiperazine (AEP)                                                                  23   --   --   --   --   --   --   --                        AEP.RIM (70/30)  --   26   --   --   --   --   --   --                        Triethylenetetramine (TETA)                                                                    --   --   12   --   --   --   --   --                        TETA.RIM (80/20) --   --   --   15   --   --   --   --                        Isophoronediamine (IPDA)                                                                       --   --   --   --   45   --   39   --                        IPDA.RIM (80/20) --   --   --   --   --   56   --   48.7                      Accelerator 399  --   --   --   --   --   --   5    5                         Glass transition temp., °C.                                                             --   108  105  132  93   114  --   --                        Pot life at 25° C.                                                     Brookfield viscosity, cps, 25°  C.                                                      1100 4190:                                                                              1830 3410 --   --   1120 3670                      Gel time, min (200 g mass)                                                                     15.8 10.8 25.6 15.0 --   --   27.4 10.4                      Peak exothermic temp., °C.                                                              258.4                                                                              235.5                                                                              236.5                                                                              232.5                                                                              --   --   216.9                                                                              204.7                     Time to peak temp., min.                                                                       19.5 14.0 30.0 18.0 --   --   30.8 14.3                      Properties of cured 1/8" Castings.sup.1                                                        5417-18A                                                     Shore D hardness, 0-10 sec                                                                     89-87                                                                              75-73                                                                              83-81                                                                              82-80                                                                              76-74                                                                              77-75                                                                              --   --                        Ultimate elongation, %                                                                         13.6 9.6  3.6  3.9  3.2  4.5  --   --                        Heat deflection temp., °C.                                                              104/110                                                                            114/119                                                                            101/110.5                                                                          107/114                                                                            84/90                                                                              90/94                                                                              --   --                        264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                 1.25 0.99 0.40 0.47 0.52 1.08 --   --                        Tensile strength, psi                                                                          1000 10200                                                                              10200                                                                              9900 9200 10600                                                                              --   --                        Tensile modulus, psi                                                                           351000                                                                             357000                                                                             407000                                                                             40300                                                                              439000                                                                             426000                                                                             --   --                        Flexural strength, psi                                                                         15000                                                                              15000                                                                              17000                                                                              17000                                                                              17000                                                                              16800                                                                              --   --                        Flexural modulus, psi                                                                          359000                                                                             355000                                                                             416000                                                                             408000                                                                             442000                                                                             442000                                                                             --   --                        Tensile shear adhesion.sup.2, psi                                                              3190 3840 --   2550 1560 --   --   --                        Peel strength.sup.2, pli                                                                       3.4  4.8  2.6  2.9  2.0  --   --   --                        __________________________________________________________________________     .sup.1 Cured 2 hrs 80° C., 3 hrs 125° C.                        .sup.2 Cured 2 hrs 110° C.                                        

With reference to Table 6 it is seen that again the extended amines ofthe present invention provided slightly softer cured epoxy resins andthat the products had higher heat deflection temperatures. It is notedthat the pot life of the systems was decreased by several minutes withthe use of the extended curing agents of the present invention.

EXAMPLE 4

Three of the amine-elastomeric polyurethane solutions (D-230.RIM 60/40,AEP.RIM 70/30 and TETA.RIM 80/20) separate into two layers upon cooling.These solutions react with phenol and formaldehyde to form MannichCondensates. The details of the Mannich Condensates that were preparedis set forth in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Mannich Condensate Prepared                                                                          Mole Ratio                                             Run #                                                                             Amine        Wt % RIM                                                                            Amine:Phenol:Formaldehyde                              __________________________________________________________________________    5465-97                                                                           N--aminoethylpiperazine                                                                    30    1:1:1                                                  5465-99                                                                           JEFFAMINE D-230                                                                            40    2:1:1                                                  5516-22                                                                           JEFFAMINE D-230                                                                            50    4:1:1                                                  5516-23                                                                           N--aminoethylpiperazine                                                                    30    2:1:1                                                  5516-24                                                                           Triethylenetetramine                                                                       30    2:1:1                                                  __________________________________________________________________________

The resulting Mannich Condensates were then used to cure epoxy resinswith the results noted in Table 8.

                                      TABLE 8                                     __________________________________________________________________________    Properties of Epoxy Resin Cured with                                          Mannich Condensates of Amine.RIM Solutions                                                            5409-41                                                                           5516-37                                                                           5516-34                                                                           5409-36                                                                           5516-12                                                                           5516-33                                                                           5409-48                                                                           5516-35                   __________________________________________________________________________    Formulation, pbw:                                                             Epoxy Resin (WPE 188)   100 100 100 100 100 100 100 100                       AEP.RIM (70/30)         26  --  --  --  --  --  --  --                        AEP.RIM (70/30) Mannich condensate (1:1:1)                                                            --  35  --  --  --  --  --  --                        AEP.RIM (70/30) Mannich condensate (2:1:1)                                                            --  --  37  --  --  --  --  --                        D-230.RIM (60/40)       --  --  --  64  --  --  --  --                        D-230.RIM (60/40) Mannich condensate (2:1:1)                                                          --  --  --  --  48  --  --  --                        D-230.RIM (50/50) Mannich condensate (4:1:1)                                                          --  --  --  --  --  66  --  --                        TETA.RIM (80/20)        --  --  --  --  --  --  15  --                        TETA.RIM (70/30) Mannich condensate (2:1:1)                                                           --  --  --  --  --  --  --  26                        Gel time, min (100 g mass)                                                                            10.8.sup.1                                                                        .sup.4                                                                            9.5 --  --  .sup.4                                                                            15.0                                                                              6.5                       Peak exothermic temp., °C.                                                                     235.5                                                                             41.6                                                                              131.8                                                                             --  --  34.2                                                                              232.2                                                                             137.6                     Time to peak temp., min.                                                                              14.0                                                                              18.6                                                                              12.7                                                                              --  --  14  18.0                                                                              8.7                       Properties of cured 1/8" Castings.sup.2                                       Shore D hardness, 0-10 sec                                                                            75-73                                                                             89-87                                                                             80-77                                                                             74-72                                                                             71-70                                                                             74-72                                                                             82-80                                                                             80-78                     Ultimate elongation, %  9.6 6.3 5.2 6.1 6.2 2.7 3.9 5.8                       Heat deflection temp., °C.                                                                     114/119                                                                           89/105                                                                            87/91                                                                             63/70                                                                             46/46                                                                             48/53                                                                             107/114                                                                           94/99                     264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                        0.99                                                                              0.24                                                                              0.38                                                                              1.03                                                                              0.13                                                                              0.30                                                                              0.47                                                                              0.22                      Tensile strength, psi   10200                                                                             10600                                                                             10100                                                                             8400                                                                              6500                                                                              7000                                                                              9900                                                                              11300                     Tensile modulus, psi    357000                                                                            401000                                                                            397000                                                                            404000                                                                            442000                                                                            399000                                                                            403000                                                                            428000                    Flexural strength, psi  15000                                                                             16900                                                                             15900                                                                             14000                                                                             9500                                                                              11000                                                                             17000                                                                             17100                     Flexural modulus, psi   335000                                                                            410000                                                                            429000                                                                            402000                                                                            449000                                                                            429000                                                                            408000                                                                            433000                    Tensile shear adhesion.sup.3, psi                                                                     3840                                                                              3360                                                                              4000                                                                              3930                                                                              --  2200                                                                              2550                                                                              2340                      Peel strength.sup.3, pli                                                                              4.8 4.6 8.9 17.7                                                                              --  6.4 2.9 2.1                       __________________________________________________________________________     .sup.1 200 g mass                                                             .sup.2 Cured 2 hrs 80° C., 3 hrs 125° C.                        .sup.3 Cured 2 hrs 110° C.                                             .sup.4 Slow viscosity increase                                           

The results, as compared with Table 6 show that the use of the MannichCondensates resulted in cure systems having lower heat deflectiontemperatures and lower impact strengths.

EXAMPLE 5

A series of extended amines was prepared by the modified procedure ofthe present invention wherein the urethane elastomers were firstdissolved in a solvent. There is no general rule that can be given as tothe identity of the solvent to be used. However, a routine proceduresuch as the one described in this example may be used as a screening aidin selecting the solvent.

The procedure used for this example is to slowly add comminutedpolyurethane elastomer to the solvent in a resin kettle and then heat toabout 150° C. to dissolve the polyurethane in the solvent. Thus,comminuted polyurethane elastomer was added to dimethylformamide in aresin kettle and the mixture was heated to a temperature of about 150°C. to dissolve the urethane. The desired amine was then added to thissolution and the dimethylformamide was stripped out by vacuumdistillation. The solutions prepared by this method are set forth inTable 9.

                  TABLE 9                                                         ______________________________________                                        Amine.RIM/DMF Solutions Prepared                                                                     Amount scrap                                                                  RIM added,                                             Run # Amine            wt %       Appearance                                  ______________________________________                                        5409-40                                                                             JEFFAMINE D-230  30         Clear, light                                                                  brown liquid                                5465-3                                                                              JEFFAMINE T-403  20         Opaque,                                                                       white liquid                                5465-6                                                                              JEFFAMINE D-400  20         Opaque,                                                                       white gel                                   5465-10                                                                             Aminoethylpiperazine                                                                           30         Cloudy, light                                                                 yellow liquid                               5465-39                                                                             Trimethylhexamethylene-                                                                        20         Cloudy, light                                     diamine                     yellow liquid                               5465-66                                                                             Isophoronediamine                                                                              20         Clear, light                                                                  yellow liquid                               ______________________________________                                    

However, when this procedure was used employing tetrahydrofuran,nonylphenol, acetone, methyl ethyl ketone, ethylene glycol monoethylether, ethylene glycol monobutyl ether and N-methylmorpholine-N-oxide,the polyurethane did not dissolve. Successful results were obtained,however, with dimethylformamide (as noted) and with diethylene glycolmonobutyl ether and diethylene glycol monoethyl ether acetate.

Dimethylformamide was used as a solvent using the above-describedprocedure with a number of amines to prepare polyurethane-aminesolutions for evaluation as epoxy curatives. The properties of thesolutions are set forth in Table 10. Properties of an epoxy resin curedwith these solutions at ambient temperatures are set forth in Tables 11and 12.

Comparisons of the analytical test results for the solutions indicatethat there was less polymer degradation by this technique than when theelastomeric polyurethane was directly dissolved in the amine asdescribed in Example 1. Again, the extended amines provided good curedepoxy resin properties. As shown by Tables 11 and 12, the products weresomewhat softer, had lower heat deflection temperatures and weregenerally more flexible than the unmodified systems. When the elevatedtemperature cures were employed, the extended systems of the presentinvention again had lower heat distortion temperature values and weresofter with the exception of the systems based upon IPDA.RIM which wereslightly harder than the system based on IPDA alone. The elevated curingexperiments are tabulated in Tables 13 and 14.

                                      TABLE 10                                    __________________________________________________________________________    Typical Analytical Analyses of Amine.RIM/DMF Solutions                        Run #      5409-68A                                                                           5409-40                                                                           5409-68C                                                                           5465-3  5465-6                                                                            5465-18                                                                           5465-10                                                                           5465-38                                                                           5465-39                                                                           5465-28C                                                                           5465-66             __________________________________________________________________________    Amine      D-230                                                                              D-230                                                                             T-403                                                                              T-403                                                                             D-400                                                                             D-400                                                                             AEP AEP TMD TMD IPDA IPDA                Wt % RIM   0    30  0    20  0   20  0   30  0   20  0    20                  Total acetylatables,                                                                     8.75 6.54                                                                              6.75 5.52                                                                              5.17                                                                              4.08                                                                              15.68                                                                             11.20                                                                             12.75                                                                             10.36                                                                             11.74                                                                              9.75                meq/g                                                                         Total amine, meq/g                                                                       8.45 5.68                                                                              6.45 5.32                                                                              4.99                                                                              3.38                                                                              23.50                                                                             15.13                                                                             12.64                                                                             10.21                                                                             11.89                                                                              9.43                1° Amine, meq/g                                                                   8.30 5.57                                                                              6.16 4.85                                                                              4.93                                                                              3.32                                                                              7.5 4.3 12.62                                                                             10.20                                                                             11.87                                                                              9.26                2° Amine, meq/g                                                                   --   --  --   --  --  --  7.03                                                                              5.36                                                                              0   0   0.01 0.17                3° Amine, meq/g                                                                   --   --  --   --  --  --  8.97                                                                              5.47                                                                              0.02                                                                              0.01                                                                              0.01 0.004               Specific gravity,                                                                        0.9480                                                                             1.0206                                                                            0.9812                                                                             100185                                                                            0.9702                                                                            1.0095                                                                            0.9879                                                                            0.9060                                                                            0.8729                                                                            0.9218                                                                            0.9261                                                                             0.9702              20/20° C.                                                              Brookfield viscosity,                                                                    --   500 --   13300                                                                             --  22500                                                                             20  800 6.0 83  23   360                 cps, 25° C.                                                            Water, wt %                                                                              0.10 0.04                                                                              0.08 0.02                                                                              0.13                                                                              0.02                                                                              0.57                                                                              0.21                                                                              0.86                                                                              0.18                                                                              0.17 0.10                __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________    Properties of Epoxy Resin Cured with Solutions of                             RIM Urethane in JEFFAMINE Polyetheramines (Ambient Curing)                                     5409-68B                                                                           5409-40B                                                                           5409-68D                                                                           5465-3B  5465-6B                              __________________________________________________________________________    Formulation, pbw                                                              Epoxy Resin (WPE 188)                                                                          100  100  100  100  100 100                                  JEFFAMINE D-230  26.4 --   --   --   --  --                                   D-230.RIM/DMF (70/30)                                                                          --   39.5 --   --   --  --                                   JEFFAMINE T-403  --   --   36.4 --   --  --                                   T-403.RIM/DMF (80/20)                                                                          --   --   --   44.5 --  --                                   JEFFAMINE D-400  --   --   --   --   45.5                                                                              --                                   D-400.RIM/DMF (80/20)                                                                          --   --   --   --   --  57.3                                 Accelerator 399  5    5    5    5    5   5                                    Gel time, min. (100 g mass)                                                                    52.0.sup.1                                                                         29.3.sup.1                                                                         27.6.sup.2                                                                         24.4.sup.2                                                                         48.1.sup.2                                                                        37.9.sup.2                           Peak exothermic temp., °C.                                                              189.5                                                                              181.1                                                                              94.3 110.2                                                                              80.9                                                                              87.3                                 Properties of Cured 1/8" Castings.sup.3                                       Shore D hardness, 0-10 sec                                                                     90-89                                                                              83-82                                                                              90-88                                                                              78-76                                                                              71-67                                                                             65- 59                               Ultimate elongation, %                                                                         2.1  4.4  1.7  5.0  20.8                                                                              100.0                                Heat deflection temp., °C.                                                              46/48                                                                              45/45.5                                                                            48/48.5                                                                            48.5/52                                                                            35/37.5                                                                           26/28                                264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                 0.23 0.31 0.42 0.60 1.45                                                                              1.97                                 Tensile strength, psi                                                                          8900 7000 7500 4600 5600                                                                              3000                                 Tensile modulus, psi                                                                           498000                                                                             442000                                                                             516000                                                                             448000                                                                             314000                                                                            179000                               Flexural strength, psi                                                                         12000                                                                              13000                                                                              16000                                                                              15000                                                                              10300                                                                             4100                                 Flexural modulus, psi                                                                          495000                                                                             441000                                                                             506000                                                                             457000                                                                             322000                                                                            155000                               Tensile shear adhesion, psi                                                                    1030 1200 1470 1380 2250                                                                              2380                                 Peel strength, pli                                                                             3.2  3.1  2.6  2.8  2.6 11.3                                 __________________________________________________________________________     .sup.1 200 g mass                                                             .sup.2 Test run at 50° C.                                              .sup.3 Cured 7 days ˜25° C.                                 

                                      TABLE 12                                    __________________________________________________________________________    Propertiesof Epoxy Resin Cured with Solutions of                              RIM Urethane in Various Amines (Ambient Curing)                                                    5465-58C                                                                           5464-10B                                                                           5465-38B                                                                           5465-39B                                                                           5465-89A                                                                           5465-66B                        __________________________________________________________________________    Formulation, pbw                                                              Epoxy Resin (WPE 188)                                                                              100  100  100  100  100  100                             N--aminoethylpiperazine (AEP)                                                                      23   --   --   --   --   --                              AEP.RIM/DMF (70/30)  --   26   --   --   --   --                              Trimethylhexamethylenediamine (TMD)                                                                --   --   18.8 --   --   --                              TMD.RIM/DMF (80/20)  --   --   --   22.2 --   --                              Isophoronediamine (IPDA)                                                                           --   --   --   --   38.5 --                              IPDA.DMF (80/20)     --   --   --   --   --   47.9                            Accelerator 399*     --   --   5    5    5    5                               Pot life at 25° C.                                                     Gel time, min. (100 g mass)                                                                        17.8 6.8  10.9 8.8  35.9 14.1                            Peak exothermic temp., °C.                                                                  171.1                                                                              142.7                                                                              146.0                                                                              142.4                                                                              128.5                                                                              127.5                           __________________________________________________________________________     *Accelerator 399 is descried in U.S. Pat. No. 4,195,143 and is a mixture      of primary, secondary and tertiary amines having an amine equivalent          weight of 65.                                                            

                                      TABLE 13                                    __________________________________________________________________________    Properties of Epoxy Resin Cured with Solutions of                             RIM Urethane in JEFFAMINE Polyetheramines                                     (Elevated Temperature Curing)                                                                  5409-68A                                                                           5409-40A                                                                           5409-68C                                                                           5465-3A                                                                            5465-37A                                                                           5465-6A                             __________________________________________________________________________    Formulation, pbw                                                              Epoxy Resin (WPE 188)                                                                          100  100  100  100  100  100                                 JEFFAMINE D-230  32   --   --   --   --   --                                  D-230.RIM/DMF (70/30)                                                                          --   46   --   --   --   --                                  JEFFAMINE T-403  --   --   42   --   --   --                                  T-403.RIM/DMF (80/20)                                                                          --   --   --   52   --   --                                  JEFFAMINE D-400  --   --   --   --   53.2 --                                  D-400.RIM/DMF (80/20)                                                                          --   --   --   --   --   67                                  Properties of Cured 1/8" Castings.sup.1                                       Shore D hardness, 0-10 sec                                                                     88-86                                                                              75-73                                                                              83-82                                                                              78-75                                                                              76-74                                                                              73-67                               Ultimate elongation, %                                                                         6.6  6.6  10.2 12.3 3.3  30.4                                Heat deflection temp., °C.                                                              80/83.5                                                                            73/79                                                                              78/82.5                                                                            70/78                                                                              46/47                                                                              33/36                               264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                 0.92 0.90 0.68 0.82 2.26 1.91                                Tensile strength, psi                                                                          9100 9300 8800 8100 7500 3100                                Tensile modulus, psi                                                                           427000                                                                             407000                                                                             395000                                                                             368000                                                                             401000                                                                             192000                              Flexural strength, psi                                                                         15000                                                                              16000                                                                              14000                                                                              14000                                                                              12600                                                                              7200                                Flexural modulus, psi                                                                          424000                                                                             399000                                                                             402000                                                                             381000                                                                             434000                                                                             264000                              Tensile shear adhesion.sup.2, psi                                                              4060 4540 3920 3660 3060 2950                                Peel strength.sup.2, pli                                                                       2.3  9.9  3.5  5.6  2.9  33.0                                __________________________________________________________________________     .sup.1 Cured 2 hrs 80° C., 3 hrs 125° C.                        .sup.2 Cured 2 hrs 110° C.                                        

                                      TABLE 14                                    __________________________________________________________________________    Propeties of Epoxy Resin Cured with Solutions of                              RIM Urethane in Various Amines (Elevated Temperature Curing)                                       5417-18A                                                                           5465-10A                                                                           5409-38A                                                                           5465-29A                                                                           5409-49A                                                                           5465-66A                        __________________________________________________________________________    Formulation, pbw                                                              Epoxy Resin (WPE 188)                                                                              100  100  100  100  100  100                             N--aminoethylpiperazine (AEP)                                                                      23   --   --   --   --   --                              AEP.RIM/DMF (70/30)  --   26   --   --   --   --                              Trimethylhexamethylenediamine (TMD)                                                                --   --   22   --   --   --                              TMD.RIM/DMF (80/20)  --   --   --   26   --   --                              Isophoronediamine (IPDA)                                                                           --   --   --   --   45   --                              IPDA.RIM/DMF (80/20) --   --   --   --   --   56                              Properties of Cured 1/8" Castings.sup.1                                       Shore D hardness, 0-10 sec                                                                         89-87                                                                              76-74                                                                              81-79                                                                              78-76                                                                              76-74                                                                              80-78                           Ultimate elongation, %                                                                             13.6 12.7 10.0 10.4 3.2  2.6                             Heat deflection temp., °C.                                                                  104/110                                                                            99.5/107                                                                           98/103                                                                             94/100                                                                             84/90                                                                              82/88                           264 psi load/66 psi load                                                      Izod impact strength, ft-lb/in                                                                     1.25 0.79 0.68 0.67 0.52 0.14                            Tensile strength, psi                                                                              10000                                                                              9300 9000 9300 9200 8500                            Tensile modulus, psi 351000                                                                             349000                                                                             324000                                                                             347000                                                                             439000                                                                             394000                          Flexural strength, psi                                                                             15000                                                                              14000                                                                              14000                                                                              14000                                                                              17000                                                                              14000                           Flexural modulus, psi                                                                              359000                                                                             359000                                                                             358000                                                                             371000                                                                             442000                                                                             424000                          Tensile shear adhesion.sup.2, psi                                                                  3190 3740 2830 3550 1560 4190                            Peel strength.sup.2, pli                                                                           3.4  6.0  2.1  3.6  2.0  3.6                             __________________________________________________________________________     .sup.1 Cured 2 hrs 80° C., 3 hrs 125° C.                        .sup.2 Cured 2 hrs 110° C.                                        

As will be seen by the foregoing specific examples, the extended aminecuring agents of the present invention provide cured epoxy systems thatare suitable for industrial applications.

It will be understood that the foregoing examples are given by way ofillustration only and not by way of limitation and that the scope of thepresent invention is defined solely by the appended claims.

What is claimed is:
 1. A method for curing a 1,2-epoxy resin whichcomprises intimately mixing said epoxy resin with an effective amount ofan amine curing agent comprising a solution of a normally solid curedpolyurethane elastomer in a 1,2-epoxy-interactive polyamine curingagent, whereby reaction of aminohydrogens of said amine with epoxygroups in said epoxy resin composition will result in the curing of saidepoxy resin.
 2. A method as in claim 1 wherein the said polyurethane isa polyurethane prepared by reaction injection molding and wherein theamine has the formula:

    H.sub.2 NC.sub.2 H.sub.4 (HNC.sub.2 H.sub.4).sub.n NH.sub.2

wherein n is a number having a value of 0 to
 5. 3. A method as in claim2 wherein n has a value of
 2. 4. A method as in claim 1 wherein the saidpolyurethane is a polyurethane prepared by reaction injection moldingand wherein the amine has the formula:

    NH.sub.2 CH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2

wherein x is a number having a value of about 2 to
 40. 5. A method as inclaim 4 wherein n has a value of about 2.6.
 6. A method as in claim 4wherein n has a value of about 5.6.
 7. A method as in claim 4 wherein nhas a value of about
 33. 8. A method as in claim 1 wherein thepolyurethane is a polyurethane prepared by reaction injection moldingand wherein the amine is an amine having the formula: ##STR6## whereinx, y and z represent numbers in the range of about 1 to 15 and x+y+zequals about 3 to
 50. 9. A method as in claim 8 where x+y+z=about 5.3.10. A method as in claim 1 wherein the polyurethane is a polyurethaneprepared by reaction injection molding and wherein the amine is an aminehaving the formula: ##STR7## wherein x and z are numbers having a valueof about 2 to 10 and y is a number having a value of about 1-50.
 11. Amethod as in claim 1 wherein the polyurethane is a polyurethane preparedby reaction injection molding and the amine is N-aminoethylpiperazine,isophoronediamine, or trimethylhexamethylenediamine.
 12. A method as inclaim 1 wherein the polyurethane is a polyurethane prepared by reactioninjection molding, wherein the amine is present as a Mannich reactionproduct of said amine, phenol and formaldehyde, and wherein said aminehas the formula:

    H.sub.2 NC.sub.2 H.sub.4 (HNC.sub.2 H.sub.4).sub.n NH.sub.2

wherein n is a number having a value of 0 to
 5. 13. A method as in claim1 wherein the polyurethane is a polyurethane prepared by reactioninjection molding and wherein said amine is present as a MannichCondensate of said amine, phenol and formaldehyde and wherein said aminehas the formula:

    NH.sub.2 CH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2

wherein x is a number having a value of about 2-40.
 14. A method as inclaim 1 wherein the polyurethane is a polyurethane prepared by reactioninjection molding, wherein the amine is N-aminoethylpiperazine and saidN-aminoethylpiperazine is present as a Mannich Condensate with phenoland formaldehyde; the mol ratio of N-aminoethylpiperazine to phenol toformaldehyde being in the range of about 1:1:1 to about 2:1:1.
 15. A1,2-epoxide resin composition prepared by curing a 1,2-epoxy resin witha 1,2-epoxy-interactive polyamine curing agent having a solidelastomeric cured polyurethane dissolved therein.
 16. A composition asin claim 15 wherein the polyurethane is a polyurethane prepared byreaction injection molding, wherein the amine is present as a MannichCondensate of said amine, phenol and formaldehyde in the mol ratio ofamine to phenol to formaldehyde in the range of about 1:1:1 to about4:1:1 and wherein the amine is an amine having the formula:

    H.sub.2 NC.sub.2 H.sub.4 (HNC.sub.2 H.sub.4).sub.n NH.sub.2

wherein n has a value of 0 to
 5. 17. A composition as in claim 15wherein the polyurethane is a polyurethane prepared by reactioninjection molding, wherein the amine is present as a Mannich Condensateof said amine, phenol and formaldehyde in a mol ratio of amine to phenolto formaldehyde to about 2:1:1 to about 4:1:1 and wherein said amine isan amine having the formula:

    NH.sub.2 CH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2

wherein n is a number having a value of about 2-40.
 18. A composition asin claim 15 wherein the polyurethane is a polyurethane prepared byreaction injection molding and wherein the amine isN-aminoethylethylpiperazine which is present as a Mannich Condensatewith phenol and formaldehyde in the mol ratio of about 1:1:1.
 19. Acomposition as in claim 15 wherein the polyurethane is a polyurethaneprepared by reaction injection molding and wherein the amine has theformula:

    H.sub.2 NC.sub.2 H.sub.4 (HNC.sub.2 H.sub.4).sub.n NH.sub.2

wherein n is a number having a value of 0 to
 5. 20. A composition as inclaim 19 wherein n has a value of about
 2. 21. A composition as in claim15 wherein the polyurethane is a polyurethane prepared by reactioninjection molding and wherein the amine has the formula:

    NH.sub.2 CH(CH.sub.3 CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2

wherein n is a number having a value of 2 to
 40. 22. A composition as inclaim 21 wherein n has a value of about 2.6.
 23. A composition as inclaim 21 wherein n has a value of about 5.6.
 24. A composition as inclaim 21 wherein n has a value of about
 33. 25. A composition as inclaim 15 wherein the polyurethane is a polyurethane prepared by reactioninjection molding and the amine is an amine having the formula: ##STR8##wherein x, y and z are numbers in the range of about 1-15 and x+y+z isfrom about 3 to
 50. 26. A composition as in claim 25 wherein x+y+z=about5.3.
 27. A composition as in claim 15 wherein the polyurethane is apolyurethane prepared by reaction injection molding and wherein theamine has the formula: ##STR9## wherein x and z are numbers havingvalues between 2 and 10 and y is a number having a value between 1 and50.
 28. A composition as in claim 15 wherein the polyurethane is apolyurethane prepared by reaction injection molding and the amine isN-aminoethylpiperazine, isophoronediamine ortrimethylhexamethylenediamine.
 29. A method for preparing a 1,2-epoxideresin which comprises the steps of:(a) heating a 1,2-epoxy-interactivepolyamine curing agent at a temperature of about 100° to about 200° C.,(b) maintaining said amine at said temperature while dissolving thereina soluble amount of a solid elastomeric cured polyurethane, (c) tothereby provide a 1,2-epoxy resin curing composition comprising asolution of said solid elastomeric polyurethane in said amine curingagent, and (d) mixing a 1,2-epoxy resin with an effective amount of saidsolution whereby reaction of amino groups in said amine with epoxygroups in said epoxy resins will result in the curing of said epoxyresin.
 30. An epoxide resin composition formed by curing a 1,2-epoxyresin with an epoxy resin curing composition comprising a1,2-epoxy-interactive polyamine curing agent having a solid elastomericcured polyurethane dissolved therein, said epoxy resin curingcomposition having been prepared by heating said amine curing agent at atemperature of about 100° to about 200° C. and maintaining said amine atsaid temperature while dissolving therein a soluble amount of said solidelastomeric polyurethane.
 31. A method for curing a compositioncomprising a 1,2-epoxy resin which consists of intimately mixing saidepoxy resin with an effective amount of an amine curing agent consistingessentially of solution of a normally solid cured polyurethane elastomerin a 1,2-epoxy-interactive polyamine curing agent, whereby reaction ofamino groups of said amine with epoxy groups in said epoxy resincomposition will result in the curing of said epoxy resin, said aminecuring agent having beein prepared by:(a) heating a1,2-epoxy-interactive polyamine curing agent at a temperature of about100° to about 200° C., (b) maintaining said amine at said temperaturewhile dissolving therein a soluble amount of a solid elastomeric curedpolyurethane, (c) to thereby provide said amine curing composition. 32.A method as in claim 31 wherein the said polyurethane is a polyurethaneprepared by reaction injection molding and wherein the amine has theformula:

    H.sub.2 NC.sub.2 H.sub.4 (HNC.sub.2 H.sub.4).sub.n NH.sub.2

wherein n is a number having a value of 0 to
 5. 33. A method as in claim32 wherein n has a value of
 2. 34. A method as in claim 31 wherein thesaid polyurethane is a polyurethane prepared by reaction injectionmolding and wherein the amine has the formula:

    NH.sub.2 CH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2

wherein x is a number having a value of about 2 to
 40. 35. A method asin claim 34 wherein n has a value of about 2.6.
 36. A method as in claim34 wherein n has a value of about 5.6.
 37. A method as in claim 34wherein n has a value of about
 33. 38. A method as in claim 31 whereinthe polyurethane is a polyurethane prepared by reaction injectionmolding and wherein the amine is an amine having the formula: ##STR10##wherein x, y and z represent numbers in the range of about 1 to 15 andx+y+z equals about 3 to
 50. 39. A method as in claim 38 wherex+y+z=about 5.3.
 40. A method as in claim 31 wherein the polyurethane isa polyurethane prepared by reaction injection molding and wherein theamine is an amine having the formula: ##STR11## wherein x and z arenumbers having a value of about 2 to 10 and y is a number having a valueof about 1-50.
 41. A method as in claim 31 wherein the polyurethane is apolyurethane prepared by reaction injection molding and the amine isN-aminoethylpiperazine, isophoronediamine, ortrimethylhexamethylenediamine.
 42. A method as in claim 31 wherein thepolyurethane is a polyurethane prepared by reaction injection molding,wherein the amine is present as a Mannich reaction product of saidamine, phenol and formaldehyde, and wherein said amine has the formula:

    H.sub.2 NC.sub.2 H.sub.4 (HNC.sub.2 H.sub.4).sub.n NH.sub.2

wherein n is a number having a value of 0 to
 5. 43. A method as in claim31 wherein the polyurethane is a polyurethane prepared by reactioninjection molding and wherein said amine is present as a MannichCondensate of said amine, phenol and formaldehyde and wherein said aminehas the formula:

    NH.sub.2 CH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2

wherein x is a number having a value of about 2-40.
 44. A method as inclaim 31 wherein the polyurethane is a polyurethane prepared by reactioninjection molding, wherein the amine is N-aminoethylpiperazine and saidN-aminoethylpiperazine is present as a Mannich Condensate with phenoland formaldehyde; the mol ratio of N-aminoethylpiperazine to phenol toformaldehyde being in the range of about 1:1:1 to about 2:1:1.